CN104105783B - The hydrotreating including integration that residue bypasses and steam pyrolysis method for directly processing crude oil - Google Patents
The hydrotreating including integration that residue bypasses and steam pyrolysis method for directly processing crude oil Download PDFInfo
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- CN104105783B CN104105783B CN201380006610.6A CN201380006610A CN104105783B CN 104105783 B CN104105783 B CN 104105783B CN 201380006610 A CN201380006610 A CN 201380006610A CN 104105783 B CN104105783 B CN 104105783B
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- 238000012545 processing Methods 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000002352 steam pyrolysis Methods 0.000 title claims abstract description 43
- 239000010779 crude oil Substances 0.000 title claims abstract description 25
- 230000010354 integration Effects 0.000 title claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000000197 pyrolysis Methods 0.000 claims abstract description 30
- 239000000295 fuel oil Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000004227 thermal cracking Methods 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 230000006835 compression Effects 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 4
- 238000006297 dehydration reaction Methods 0.000 claims 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 14
- 239000003208 petroleum Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 25
- 150000002430 hydrocarbons Chemical class 0.000 description 18
- 239000004215 Carbon black (E152) Substances 0.000 description 17
- 238000005204 segregation Methods 0.000 description 17
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000007599 discharging Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000571 coke Substances 0.000 description 9
- 238000010791 quenching Methods 0.000 description 9
- 230000000171 quenching effect Effects 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002737 fuel gas Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- -1 ethylene, propylene, butylene Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 101000775932 Homo sapiens Vesicle-associated membrane protein-associated protein B/C Proteins 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 102100032026 Vesicle-associated membrane protein-associated protein B/C Human genes 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920006216 polyvinyl aromatic Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0217—Separation of non-miscible liquids by centrifugal force
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0042—Degasification of liquids modifying the liquid flow
- B01D19/0052—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused
- B01D19/0057—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused the centrifugal movement being caused by a vortex, e.g. using a cyclone, or by a tangential inlet
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/16—Preventing or removing incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provide a kind of for include steam pyrolysis district that the hydrogenation processing district that residue bypasses is integrated mutually, with allow directly processing crude oil material so that the method producing the petroleum chemicals including alkene and aromatic compound.For directly processing crude oil to produce olefinic and including with steam pyrolysis method with the hydrotreating of the described integration of aromatic base crude oil chemical products: described crude separation is become light components and heavy component；Described light components and hydrogen are fed to the hydrogenation processing district of operation under conditions of being effective in the effluent producing hydrogenation processing；Make the effluent product stream that thermal cracking mixes in the case of there is steam of described hydrogenation processing with generation；Separate the product stream of described mixing；Hydrogen that purification reclaims from the product stream of described mixing and it is recycled to described hydrogenation processing district；Flow back to receive alkene and aromatic compound from the mix products of described separation；And reclaim the pyrolysis fuel oil of the mix products stream from described separation and the combination stream of the heavy component from step (a) as fuel oil blend.
Description
Related application
This application claims the rights and interests of the U.S. Provisional Patent Application No. 61/591,816 submitted on January 27th, 2012, described
The disclosure of application is incorporated herein in its entirety by reference.
Background of invention
Invention field
The present invention relates to a kind of for directly processing crude oil to produce petroleum chemicals such as alkene and aromatic compound
The hydrotreating of integration and steam pyrolysis method.
Description of Related Art
Light alkene (that is, ethylene, propylene, butylene and butadiene) and aromatic compound (that is, benzene, toluene and two
Toluene) it is widely used basic intermediate in petrochemistry and chemical industry.Thermal cracking or steam pyrolysis are for generally to deposit
In the case of steam and do not depositing in the case of oxygen for forming the major type of method of these materials.For water
The raw material of steam pyrolysis can include oil gas and distillation such as Petroleum, kerosene and gas oil.Obtaining of these raw materials
Property be typically limited and need the expensive and method step of energy-intensive in crude oil refineries.
Heavy hydrocarbon has been used to be studied as the raw material of steam pyrolysis reactor.Conventional heavy hydrocarbon pyrolysis operations
In major defect be coke formed.Such as, the steam pyrolysis method for heavy liquid hydrocarbon is disclosed in U.S. Patent number 4,
In 217,204, wherein it is incorporated into the spray of fused salt in steam pyrolysis reaction zone to attempt to minimize coke formation.Make
With in an example of the Arabian light crude of the Conradson carbon residue with 3.1 weight %, cracking apparatus can exist
Ongoing operation 624 hours in the case of fused salt.Without in the comparison example of fused salt, steam pyrolysis reactor is little only 5
Time after due in reactor the formation of coke and become clogged up and inoperable.
Additionally, use heavy hydrocarbon as the alkene of the raw material of steam pyrolysis reactor and the productivity of aromatic compound and
Distribution is different from those using hydrocarbon feedstock.Heavy hydrocarbon has the aromatic content higher than light hydrocarbon, as by relatively
Indicated by high Bureau of Mines Correlation index (BMCI).BMCI is the tolerance of the armaticity of raw material and is calculated as follows:
BMCI=87552/VAPB+473.5* (sp.gr.)-456.8 (1)
Wherein:
VAPB=volume average boiling point in terms of rankine degree (degrees Rankine), and
The proportion of sp.gr.=raw material.
Along with BMCI reduces, ethylene yield expection increases.Therefore, for steam pyrolysis, highly paraffinic or low virtue
Fragrant compounds of group charging is typically preferably, thus obtains the required alkene of higher yields and avoid higher unwanted product
Coke in thing and reactor coil section is formed.
Absolute coke synthesis speed in steam pyrolysis device by Cai et al., " Coke Formation in Steam
Crackers for Ethylene Production, " Chem.Eng.&Proc., volume 41, (2002), 199-214 is carried out
Report.In general, absolute coke synthesis speed is according to alkene > aromatic compound > incremental order of alkane, wherein alkene
Hydrocarbon represents heavy olefins.
In order in response to the demand of the growth to these petroleum chemicals, it is possible to other class of relatively large acquisition
The charging of type such as crude oil is attractive for Producer.Use crude oil feeding will minimize or eliminate refinery at these
The production of petroleum chemicals occurs the probability of bottleneck.
Although steam pyrolysis method well develops and be suitable for its predetermined purpose, but the selection of raw material has the most very much
Limit.
Summary of the invention
System and method herein provides steam pyrolysis that is a kind of and that include that the hydrogenation processing district that residue bypasses is integrated
District is to allow directly processing crude oil material to produce petroleum chemicals, including alkene and aromatic compound.
Steam with the hydrotreating and water producing the integration of olefinic and aromatic base crude oil chemical products for directly processing crude oil
Gas method for pyrolysis includes: described crude separation is become light components and heavy component；Described light components and hydrogen are fed and extremely exists
Being effective in the hydrogenation processing district operated under conditions of producing the effluent of hydrogenation processing, the effluent of described hydrogenation processing has fall
Low pollutant load, the paraffinicity of increase, the Bureau of Mines Correlation index of reduction and the american petroleum of increase
Can proportion；Make described hydrogenation processing effluent in the case of there is steam thermal cracking in case produce mixing product stream；
Separate the product stream of described mixing；Hydrogen that purification reclaims from the product stream of described mixing and it is recycled to described hydrogenation adds
Work area；Flow back to receive alkene and aromatic compound from the mix products of described separation；And reclaim the mixing from described separation
The pyrolysis fuel oil of product stream and the combination stream of heavy component from step (a) are as fuel oil blend.
As used herein, term " crude oil " should be read to include the whole crude from usual sources, has been subjected to
The crude oil of pretreatment.Term crude oil will also be understood to include and is already subjected to water-separating of oil and/or gas-separating of oil and/or desalination
And/or the crude oil of stabilisation.
The other side of the method for the present invention, embodiment and advantage are discussed further below.Further, it should be understood that it is aforementioned
Information with described below be the most only the illustrative example of various aspect and embodiment, and aim to provide for understanding required
The feature of protection and the character of embodiment and the general survey of characteristic or framework.Accompanying drawing is illustrative and is provided to further
Understand different aspect and the embodiment of the method for the present invention.
Accompanying drawing is sketched
The present invention will be following and be explained in further detail referring to the drawings, wherein:
Fig. 1 is the method flow diagram of the embodiment of integration method described herein；And
Fig. 2 A to Fig. 2 C is some embodiment according to the steam pyrolysis unit in integration method described herein
Used in the exemplary illustration that carries out of the perspective view of vapor-liquid segregation apparatus, top view and side view.
Detailed Description Of The Invention
Figure 1 illustrates the hydrogenation processing and steam pyrolysis method and system including that there is the integration of residue bypass
Flow chart.The system of described integration generally comprises charging Disengagement zone 20, selective catalytic hydrogenation processing district, steam pyrolysis district
30 and product Disengagement zone.
Charging Disengagement zone 20 includes the entrance for receiving raw material stream 1, for discharging the outlet of the part 22 of discharge, and
For discharging the outlet of residual hydrocarbon part 2.Cut point in Disengagement zone 20 may be set so that it is blended with residual fuel oil
Thing is compatible, e.g., from about 540 DEG C.Disengagement zone 20 can be single-stage segregation apparatus, such as flash separator.
In further embodiment, Disengagement zone 20 can include eddy flow phase-separating device or based on steam and the thing of liquid
Reason or other segregation apparatus of mechanical separation or consisting essentially of (that is, in the case of there is not flash zone operate).Steam
One example of solution-air body segregation apparatus by and illustrate with reference to Fig. 2 A to Fig. 2 C.The class of vapor-liquid segregation apparatus
Being also described in U.S. Patent Publication number 2011/0247500 like arrangement, described patent is incorporated herein in its entirety by reference.
Include in described Disengagement zone based on steam and the segregation apparatus being physically or mechanically separated of liquid or consisting essentially of reality
Executing in scheme, cut point can be adjusted based on the fluid velocity of gasification temperature and the material entering device.
Selective hydrogenation processing district includes the hydrogenation processing reaction zone 4 with entrance, and described entrance is used for receiving hydrocarbon part
21 with the mixture 3 of hydrogen 2 from steam pyrolysis product stream recirculation and supplement hydrogen when necessary.Hydrogenation processing reaction zone 4 is entered
One step includes the outlet of the effluent 5 for discharging hydrogenation processing.
Reactor effluent 5 from the one or more hydrogenation processing reactor enters in heat exchanger (not shown)
Row cools down and delivers to high-pressure separator 6.Separator headpiece 7 is cleaned and obtained rich in hydrogen in amine unit 12
Gas stream 13 be passed to recycle compressor 14 to be used as recirculation gas 15 in described hydrogenation processing reactor.Come
Carry out cooling down and be introduced to low pressure cold separator 9 from the bottoms 8 in generally liquid form of high-pressure separator 6,
Described in described low pressure cold separator, bottoms is separated into gas stream and liquid stream 10.Gas from low pressure cold separator
Including hydrogen, H2S、NH3And any light hydrocarbon such as C1-C4Hydrocarbon.Generally these gases are conveyed to be processed further such as burning processing
(flare processing) or fuel gas are processed.According to some embodiment herein, by hydrogen, H will be comprised2S、NH3With
And any light hydrocarbon such as C1-C4Water vapor gas stream 11 and the steam pyrolysis device product 44 of hydrocarbon are combined to reclaim hydrogen.Liquid
Stream 10 all or part of be used as steam pyrolysis district 30 charging.
Steam pyrolysis district 30 generally comprises convection section 32 and pyrolysis section 34, and described pyrolysis section can based on this area
The steam pyrolysis unit known operates, i.e. by the most described for thermal cracking feed charge in the case of there is steam
Convection section.Additionally, in some optional embodiment as described herein (as indicated by FIG with dotted line), steam
Between solution-air body segregation section 36 section of being included in 32 and section 34.Steam pyrolysis charging from the heating of convection section 32 is passed through
Vapor-liquid segregation section 36 can be the segregation apparatus being physically or mechanically separated based on steam and liquid.
In one embodiment, vapor-liquid segregation apparatus by and illustrate with reference to Fig. 2 A to Fig. 2 C.Steam
The similar arrangement of solution-air body segregation apparatus is also described in U.S. Patent Publication number 2011/0247500, and described patent is to quote
Mode be integrally incorporated herein.In this device, steam and liquid pass through with the flowing of eddy flow geometry, the most described device
Isothermally and operate under the low-down time of staying.In general, steam with circular pattern vortex to produce power, the most relatively
The drop of weight and liquid are captured and are directed across to liquid outlet as fuel oil 38, and such as, it is added into pyrolysis combustion
Expect oil blend, and steam is guided through the vapor outlet port charging 37 as pyrolysis section 34.Gasification temperature and fluid velocity
It is altered to adjust approximate temperature separation, compatible with residual fuel oil blend the most in certain embodiments, e.g., from about
540℃。
Quenching district 40 includes that the outlet with steam pyrolysis district 30 is in the entrance of fluid communication, for allowing quenching solution
42 enter entrances, for discharge quenching mixing product stream 44 outlet and for discharging the outlet of quenching solution 46.
In general, the middle product stream 44 through the mixing of quenching is converted to intermediate product stream 65 and hydrogen 62, and hydrogen exists
The inventive method is purified and is used as recycle hydrogen air-flow 2 in hydrogenation processing reaction zone 4.Intermediate product stream 65 is usual
Being fractionated into end product and residue in Disengagement zone 70, described Disengagement zone can be one or more separative element, as multiple
Fractionating column, including dethanizer, depropanizing tower and debutanizing tower, the most as one of ordinary skill in the art known in.
Such as, the equipment being suitable for is described in " Ethylene, " Ullmann ' s Encyclopedia of Industrial
Chemistry, volume 12, page 531 to page 581, specifically in Figure 24, Figure 25 and Figure 26, described document is to quote
Mode is expressly incorporated herein.
In general, product Disengagement zone 70 includes being in fluid communication with product stream 65 and multiple product exit 73 to 78
Entrance, the plurality of product exit includes the outlet 78 for discharging methane, for discharging the outlet 77 of ethylene, for discharging third
The outlet 76 of alkene, for discharging the outlet 75 of butadiene, for discharging the outlet 74 of the butylene of mixing and for discharging pyrolysis
Vapour oil outlet 73.Further it is provided that for the outlet discharging pyrolysis fuel oil 71.Part from the discharge of charging Disengagement zone 20
22 and part 38 optionally from the discharge of vapor-liquid segregation section 36 is combined with pyrolysis fuel oil 71 and the stream that mixes
Can be drawn out of as pyrolysis fuel oil blend 72, such as, stay in and non-at-scene refinery is processed further or is used as
Low sulphur fuel oil blend for the fuel in optional generating district 120.It should be noted that though it is shown that six products exports, can
Less or more products are provided to go out to depend on the arrangement of separative element that (such as) used and yield and Spreading requirements
Mouthful.
Can provide optional generating district 120, it includes the entrance for receiving fuel oil 72 and for discharging remainder
Divide the outlet of the raw material of below the standard quality that such as hydrogen is not enough.Optional fuel gas desulfurization zone 120 includes for receiving
The entrance of the remainder in self power generation district 110 and for discharging the outlet of the fuel gas of desulfurization.
In using the embodiment of method of the arrangement shown in Fig. 1, crude oil material 1 is introduced in charging Disengagement zone 20
To produce the part 22 and remaining hydrocarbon part 21 discharged.The hydrogen 2 and 15 of hydrocarbon part 21 and effective dose (and if desired, is mended
Be flushed with hydrogen source) carry out mixing forming the stream 3 of combination, and mixture 3 in 300 DEG C to 450 DEG C scopes at a temperature of feed to
The entrance of selective hydrogenation processing reaction zone 4.In certain embodiments, hydrogenation processing reaction zone 4 includes as owned together
U.S. Patent Publication number 2011/0083996 and PCT Patent Application publication No. WO2010/009077, WO2010/009082,
One or more unit operation described in WO2010/009089 and WO2009/073436, described patent is all to quote
Mode is integrally incorporated herein.Such as, hydrogenation processing district can include one of the Hydrodemetalation catalyst containing effective dose or
Multiple beds, and containing effective dose there is adding of Hydrodearomatization, hydrodenitrogeneration, hydrodesulfurization and/or hydrocracking function
One or more beds of hydrogen processing catalyst.In further embodiment, hydrogenation processing district 200 includes more than two catalyst
Bed.In other embodiments, hydrogenation processing reaction zone 4 includes the catalysis each containing one or more (such as) difference in functionality
Multiple reaction vessels of agent bed.
Hydrogenation processing reaction zone 4 makes crude oil material HDM, Hydrodearomatization, hydrodenitrogeneration, adds being effective in
Operate under the parameter of hydrogen desulfurization and/or hydrocracking.In certain embodiments, following condition is used to carry out hydrogenation processing:
Operation temperature in 300 DEG C to 450 DEG C scopes；Operation pressure in 30 bars to 180 bar scopes；And at 0.1h-1To 10h-1
Liquid hourly space velocity (LHSV) in scope.It should be noted that and demonstrate the advantage using crude oil as the raw material in hydrogenation processing district, example
As, as compared with the identical hydrogenation machining cell operation that atmospheric residue is used.Such as, in 370 DEG C to 375 DEG C scopes
Initiate or under running temperature, deactivation rate is about 1 DEG C/month.By contrast, if residue is treated processed, then deactivation rate will
Closer to about 3 DEG C/month to about 4 DEG C/month.The pressure processing generally employing about 200 bars of atmospheric residue, and process the basis of crude oil
The method of invention can operate under the pressure of as little as 100 bars.It addition, for the Gao Shui needed for the increase of the hydrogen content realizing charging
Flat saturation, when compared with atmospheric residue, this method can operate under high flux.LHSV can be up to 0.5, and normal pressure
The LHSV of residue is usually 0.25.Have now surprisingly been found that and be, when process crude oil time deactivation rate direction with generally seen
Observe is in opposite direction.At small throughput (0.25hr-1Inactivation under) is 4.2 DEG C/month and at more high flux (0.5hr-1) under
Inactivation is 2.0 DEG C/month.Use the every kind of charging considered in the industry, it was observed that contrary situation.This is due to urge
The cleaning function of agent.
Reactor effluent 5 from hydrogenation processing district 4 carries out cooling down and delivering to high pressure in exchanger (not shown)
Cold or heat separator 6.Separator headpiece 7 is cleaned and obtained gas stream 13 quilt rich in hydrogen in amine unit 12
It is transferred to recycle compressor 14 to be used as recirculation gas 15 in hydrogenation processing reaction zone 4.Coming in generally liquid phase
Carry out cooling down and being then introduced to low pressure cold separator 9 from the separator bottom thing 8 of high-pressure separator 6.Comprise hydrogen, H2S、NH3
And any light hydrocarbon (it can include C1-C4Hydrocarbon) residual gas stream 11 can purge out also from low pressure cold separator routinely
And send to and be processed further, such as burning processing or fuel gas processing.In some embodiment of the method for the present invention, pass through
Stream 11 (as indicated by the dashed line) is combined with the cracked gas stream 44 from steam pyrolysis device product and reclaims hydrogen.
The effluent 10 of hydrogenation processing comprises pollutant (that is, metal, sulfur and the nitrogen) content of reduction, the alkane of increase
Content, the BMCI of reduction and American Petroleum Institute (API) (API) proportion increased.
There is the steam (such as allowing entrance via steam entry) of effective dose in the effluent 10 of hydrogenation processing
In the case of be transported to the entrance of convection section 32.In convection section 32, mixture is heated to predetermined temperature, such as, uses
One or more waste heat flux or other heating arrangement being suitable for.Pyrolysis feed stream is passed with the mixture through heating of steam
It is handed to pyrolysis section 34 to produce the product stream 39 of mixing.In certain embodiments, the mixture of heating from section 32 is made
By vapor-liquid segregation section 36, wherein part 38 is discharged as the fuel line of oils being suitable for being blended with pyrolysis fuel oil 71
Point.
Steam pyrolysis district 30 makes effluent 4 be cracked into required product (to include ethylene, propylene, butadiene, mixed being effective in
Close butylene and pyrolysis gasoline) parameter under operate.In certain embodiments, following condition is used to carry out steam pyrolysis:
With the temperature in 400 DEG C to 900 DEG C scopes in pyrolysis section in convection section；The steam of 0.3:1 to 2:1 scope and hydrocarbon in convection section
Ratio；And the time of staying in 0.05 second to 2 seconds scope in convection section and in pyrolysis section.
In certain embodiments, vapor-liquid segregation section 36 includes one or more steaming as shown in Fig. 2 A to 2C
Gas-liquid segregation apparatus 80.Vapor liquid segregation apparatus 80 is operation economy and Maintenance free, because it need not electricity
Power or chemistry supply.In general, device 80 includes three ports, including the arrival end for receiving vapour-liquid mixture
Mouthful, be respectively used to discharge and collect the steam that separated and the vapor outlet port port of liquid and fluid outlet port.Device 80 base
Combination in following phenomenon operates, and the linear velocity including the mixture entered changes into rotation by overall situation flowing pre-rotation section
Rotary speed, it is used for making the controlled centrifugal action of steam and liquid (residue) pre-separation and is used for promoting that steam is (residual with liquid
Excess) the cyclonic action of separation.In order to obtain these effects, device 80 includes pre-rotation section 88, controlled eddy flow vertical section
90 and liquid header/settling section 92.
As shown in Figure 2 B, the controlled pre-rotation element that pre-rotation section 88 is included between cross section (S1) and cross section (S2)
And be connected with controlled eddy flow vertical section 90 and be positioned at the connecting element between cross section (S2) and cross section (S3).Straight from having
The vapor liquid mixture of the entrance 32 in footpath (D1) is at the tangential access arrangement in cross section (S1) place.According to below equation, enter stream
At least the 10% of the area that area is entrance 82 of approach section (S1):
Pre-rotation element 88 defines curvilinear flow path and it is characterized by from entrance section S1 constant to outlet S2
, reduce or increase cross section.Ratio between outlet (S2) and the entrance section (S1) of controlled pre-rotation element
In certain embodiments in the scope of 0.7≤S2/S1≤1.4.
The rotary speed of mixture depends on the radius of curvature (R1) of the centrage of pre-rotation element 88, wherein said center
Line is defined as linking the curved lines of all central points of the continuous cross-sections surfaces of pre-rotation element 88.In some embodiment
In, radius of curvature (R1) is in the scope of 2≤R1/D1≤6, and wherein angular aperture is in the scope of 150 °≤α R1≤250 °.
Although being depicted as the most foursquare, but the cross sectional shape at entrance S1 can be rectangle, round rectangle,
Circle, oval or other linear, shaped form or the combination of above-mentioned shape.In certain embodiments, pass through along fluid
Shape (such as) square shape on the whole in the cross section of the curved path of pre-rotation element 88 is changed to rectangle shape progressively
Shape.The cross section of element 88 is changing into rectangular shape progressively advantageously makes aperture area maximize, thus allows gas in early days
Stage separates and obtains uniform VELOCITY DISTRIBUTION with liquid mixture, and makes the shear stress in fluid flowing minimize.
From controlled pre-rotation element 88 fluid stream from cross section (S2) through section (S3) by described connecting element to
Reach controlled eddy flow vertical section 90.Described connecting element includes for that open and be connected in controlled eddy flow vertical section 90
Entrance or the open area integral with it.Fluid stream enters controlled eddy flow vertical section 90 at a high rotational speed to produce rotation
Stream effect.Ratio between connecting element outlet (S3) and entrance section (S2) is in certain embodiments at 2≤S3/S1
In the scope of≤5.
Mixture enters eddy flow vertical section 90 at a high rotational speed.Kinetic energy reduce and steam under cyclonic action with liquid
Body separates.Eddy flow is formed in the upper level 90a and lower horizontal 90b of eddy flow vertical section 90.In upper level 90a, mixed
Compound is characterized with high vapor concentration, and in lower horizontal 90b, mixture is characterized with high strength of fluid.
In certain embodiments, the internal diameter D2 of eddy flow vertical section 90 is in the range of 2≤D2/D1≤5 and along its height
Degree can be constant, and the length (LU) of upper part 90a is in the range of 1.2≤LU/D2≤3, and the length of low portion 90b
Degree (LL) is in the range of 2≤LL/D2≤5.
The end close to vapor outlet port 84 of eddy flow vertical section 90 is connected to the release riser that partially opens and connects
Pyrolysis section to steam pyrolysis unit.The diameter (DV) of the release riser partially opened is in certain embodiments 0.05
In the scope of≤DV/D2≤0.4.
Therefore, in certain embodiments, and the characteristic of mixture entered is depended on, large volume fraction therein
Steam is by having the release pipe partially opened of diameter DV from exporting 84 separating devices 80.There is low vapor concentration or do not deposit
Liquid phase (such as, residue) at vapor concentration is left by the base section with cross section S4 of eddy flow vertical section 90,
And it is collected in liquid header and sedimentation pipe 92.
Join domain between eddy flow vertical section 90 and liquid header and sedimentation pipe 92 has in certain embodiments
The angle of 90 °.In certain embodiments, the internal diameter of liquid header and sedimentation pipe 92 in the scope of 2≤D3/D1≤4 also
And be constant across duct length, and the scope that the length (LH) of liquid header and sedimentation pipe 92 is in 1.2≤LH/D3≤5
In.There is the liquid of low vapor volume mark by there is diameter DL and being positioned at the bottom of described sedimentation pipe or close to bottom it
The pipeline 86 at place is removed from equipment, and described diameter DL is in certain embodiments in the scope of 0.05≤DL/D3≤0.4.
Although various components are described and have single part dividually, but those of ordinary skill in the art
Should be understood that equipment 80 is formed as an overall structure, such as, it can be casting or molding, or it can be from individually
Part assemble, such as, by welding or otherwise single parts are attached together, described part may
Or may inaccurately correspond to component described herein and part.
Although it should be understood that various sizes are listed as diameter, but these values are not cylindrical reality in described component parts
Executing in scheme can also be equivalent diameter.
The product stream 39 of mixing is passed to the entrance in quenching district 40, wherein quenching solution 42 (such as, water and/or pyrolysis
Fuel oil) introduce via single entrance, to produce middle the mixing through quenching of the temperature (e.g., from about 300 DEG C) with reduction
Close product stream 44, and useless quenching solution 46 is discharged.Admixture of gas effluent 39 from cracker is typically hydrogen, first
The mixture of alkane, hydrocarbon, carbon dioxide and hydrogen sulfide.After cooling down with water or oil hardening, mixture 44 is in compound compressor district
It is compressed (in usual 4 to 6 grades) in 51 producing the admixture of gas 52 of compression.The admixture of gas 52 of compression is at caustic alkali
Processing unit 53 is carried out process to produce the admixture of gas 54 exhausting hydrogen sulfide and carbon dioxide.Admixture of gas 54 is in pressure
Suo Ji district 55 compresses further, and obtained cracked gas 56 generally stands K cryogenic treatment to take off in unit 57
Water, and by using molecular sieve to be further dried.
Cold cracked gas stream 58 from unit 57 is passed to domethanizing column 59, produces containing from institute from this tower
State the hydrogen of cracked gas stream and the overhead stream 60 of methane.Then bottoms 65 from domethanizing column 59 is conveyed at product
Disengagement zone 70 is processed further, and described product Disengagement zone includes multiple fractionating column, including dethanizer, depropanizing tower and de-fourth
Alkane tower.The technique with the domethanizing column of different order, dethanizer, depropanizing tower and debutanizing tower can also be used to join
Put.
According to methods herein, with methane separation and in unit 61 after hydrogen retrieval at domethanizing column 59, it is thus achieved that tool
There is the hydrogen 62 of the purity of usual 80 volume %-95 volume %.Recovery method in unit 61 include low temperature reclaim (such as, about-
At a temperature of 157 DEG C).Then hydrogen stream 62 be passed to hydrogen purification unit 64, such as pressure-variable adsorption (PSA) unit, to obtain tool
There is the hydrogen stream 2 of 99.9%+ purity；Or film separation unit, to obtain the hydrogen stream 2 with about 95% purity.The hydrogen of purification
Then stream 2 be recycled back the major part of the required hydrogen for use as hydrogenation processing district.Additionally, small scale may be used for acetylene,
The hydrogenation (not shown) of propine and allene.Additionally, according to methods herein, methane stream 63 can optionally recirculation
To be used as burner and/or the fuel of heater to steam pyrolysis device.
Bottoms 65 from domethanizing column 59 is transported to the entrance of product Disengagement zone 70 to be separated into respectively
Methane, ethylene, propylene, butadiene, the butylene of mixing and pyrolysis vapour via outlet 78,77,76,75,74 and 73 discharge
Oil.Pyrolysis gasoline generally comprises C5-C9 hydrocarbon, and can extract benzene, toluene and dimethylbenzene from this section of fraction.From charging
The part 22 of the discharge of Disengagement zone 100 and the heavy liquid fraction 38 not gasified optionally from vapor-liquid segregation section 36
With pyrolysis fuel oil 71 (such as, the boiling at a temperature of the boiling point higher than minimum boiling point C10 compound from Disengagement zone 70
Material, is referred to as " C10+ " stream) combine, and this combination is drawn out of as pyrolysis fuel oil blend 72 such as so that non-existing
Field refinery (not shown) is processed further.
In the embodiment that some is optional, fuel oil 72 district 110 that can be transferred to generate electricity generates electricity and (such as can use combustion
Material oil 72 is as one or more steamturbines of fuel source), and remainder is transported to fuel gas desulfurization zone 120
To produce the fuel gas of desulfurization.
Include the improvement being hydrogenated with processing district relative to the advantage of the system of Fig. 1 description, wherein said method can be effectively
It is used for improving the hydrogen content of product.Such as, system described herein uses the hydrotreating catalyst with smaller aperture due, and this promotees
The activity making hydrotreating react is the biggest.It addition, total hydrogen consumption in hydrotreating district significantly reduces.Hydrogen does not consume and carries
Rise undersaturated heavy residue, but for carrying out the fraction of pyrolytic reaction, such as at 540 DEG C of fractions boiled below.Example
As more than 540 DEG C, the heavier fraction of boiling generates electricity for factory, and remainder is recovered as fuel oil.
In certain embodiments, selective hydrogenation processing or hydrotreating method can pass through aromatic compound (especially
It is polyvinyl aromatic compound) saturated, then gentle hydrocracking (or reduce to the paraffinicity increasing raw material
BMCI).When hydrotreating crude oil, pollutant such as metal, sulfur and nitrogen can be by making raw material by the de-gold of a series of execution
The layered catalyst of the catalysis of genusization, desulfurization and/or denitrogenation is removed.
In one embodiment, it is used for carrying out catalyst suitable of hydrodemetallisation (HDM) and hydrodesulfurization (HDS)
Sequence is as follows:
A. hydrodemetallisation catalyst.Catalyst in HDM section is generally based on λ alumina support, has about 140-
240m2The surface area of/g.This catalyst is best described as having the highest pore volume, such as, more than 1cm3/g.Hole
Gap size itself is usually predominantly macropore.Require that this point is to provide the metal on catalyst surface and optional adulterant to take the photograph
The Large Copacity taken.The generally nickel that active metal is proportionally Ni/Ni+Mo < 0.15 on catalyst surface and the sulfide of molybdenum.
The concentration of nickel is lower than other catalyst on HDM catalyst, because some nickel and vanadium are it is contemplated that from raw material itself in removal process
Deposition, thus serve as catalyst.The adulterant used can be that one or more phosphorus (see, e.g., U.S. Patent Publication number
US2005/0211603, it is hereby incorporated herein by), boron, silicon and halogen.Catalyst can be to extrude in aluminium oxide
Thing or the form of alumina beads.In certain embodiments, alumina beads will at the top of bed for absorbing at metal
The unloading of the catalyst HDM bed in promotion reactor when the scope of 30% to 100%.
B. Intermediate Catalyst can be used for carrying out the transition between HDM and HDS function.It has intermetallic metal load and
Pore size distribution.Catalyst in HDM/HDS reactor is substantially the carrier based on aluminium oxide in extrudate form,
It is optionally present at least one catalytic metal (such as, molybdenum and/or tungsten) from group vi, and/or from group VIII extremely
Few a kind of catalytic metal (such as, nickel and/or cobalt).Described catalyst the most optionally comprise at least one selected from boron, phosphorus, halogen with
And the adulterant of silicon.Physical characteristic includes about 140-200m2The surface area of/g, at least 0.6cm3The pore volume of/g and be mesopore
And the hole in 12 to 50nm scope.
Catalyst in c.HDS section can include having those of carrier material based on gamma-alumina, has towards HDM model
The typical surface area of the higher-end enclosed, e.g., from about 180-240m2The scope of/g.This required higher surface of HDS produces phase
To less pore volume, such as, less than 1cm3/g.Described catalyst comprises at least one element (such as molybdenum) from group vi
With at least one from the element (such as nickel) of group VIII.Described catalyst also comprises at least one selected from boron, phosphorus, silicon and halogen
The adulterant of element.In certain embodiments, cobalt is for providing the most high-caliber desulfurization.The metal load of activity phase is relatively
High because required activity is higher, so make the mol ratio of Ni/Ni+Mo in the scope of 0.1 to 0.3, and (Co+Ni)/
Mo mol ratio is in the scope of 0.25 to 0.85.
D. final catalyst (its optionally substitute second and the 3rd catalyst) be designed to carry out raw material hydrogenation (and
It is not the major function of hydrodesulfurization), such as such as Appl.Catal.A General, described in 204 (2000) 251.Described
Catalyst also will be promoted by Ni and carrier will be macropore gamma-alumina.Physical characteristic includes the higher-end towards HDM scope
Surface area, such as 180-240m2/g gr.This required higher surface of HDS produces relatively small pore volume, example
As, less than 1cm3/g。
Methods herein and system provide the improvement being better than known steam pyrolysis cleavage method:
Use crude oil as raw material to produce petroleum chemicals such as alkene and aromatic compound；
The hydrogen content of the charging in steam pyrolysis district is enriched with for the alkene of high yield；
Coke precursors is significantly removed from initial whole crude, and this allows the coke reduced in radiant coil to be formed；And
Additionally impurity such as metal, sulfur and nitrogen compound is also significantly removed from initial charge, and this avoids end product
Post processing.
Additionally, the hydrogen produced from steam pyrolysis district is recycled to be hydrogenated with processing district, to minimize the demand to fresh hydrogen.
In certain embodiments, the system of integration described herein only needs fresh hydrogen to start operation.Once reaction reaches flat
Weighing apparatus, hydrogen purification system can provide enough high-purity hydrogens, to maintain the operation of whole system.
The method and system of the present invention is had been described in above and appended accompanying drawing；But, general for this area of amendment
Will be apparent from for logical technical staff, and protection scope of the present invention will be limited by claims below.
Claims (8)
1. one kind is used for hydrotreating and the water directly processing crude oil to produce the integration of olefinic and aromatic base crude oil chemical products
Steam method for pyrolysis, described method includes:
A. described crude separation is become light components and heavy component；
B. described light components and hydrogen are fed to the hydrogenation of operation under conditions of being effective in the effluent producing hydrogenation processing
Processing district；
C. the effluent product stream that thermal cracking mixes in the case of there is steam of described hydrogenation processing is made with generation；
D. the mix products stream of described thermal cracking is separated；
E. it in the middle hydrogen reclaimed of step (d) and is recycled to step (b) by purification；
F. the mix products from described separation flows back to receive alkene and aromatic compound；And
G. the pyrolysis fuel oil of the mix products stream from described separation and the combination stream of the heavy component from step (a) are reclaimed
As fuel oil blend.
2. the hydrotreating integrated as claimed in claim 1 and steam pyrolysis method, it farther includes
Described hydrogenation processing district reactor effluent is separated to reclaim in high-pressure reactor
Cleaned and be recycled to the described hydrogenation processing district gas part as other hydrogen source；With
Liquid portion；And
In low pressure separator, the described liquid portion from described high-pressure separator is separated into gas part and liquid portion,
Wherein the described liquid portion from described low pressure separator is the effluent of the described hydrogenation processing standing thermal cracking, and
And from the separation after described steam pyrolysis district and in step (d) of the described gas part of described low pressure separator
It is combined with the described product stream mixed before.
3. the hydrotreating integrated as claimed in claim 1 and steam pyrolysis method, wherein said cracking step includes
The effluent of heating hydrogenation processing in the convection section in steam pyrolysis district,
The effluent of the hydrogenation processing of described heating is separated into vapor fraction and liquid distillate,
Described vapor fraction is transferred to the pyrolysis section in steam pyrolysis district, and
Discharge described liquid distillate.
4. the hydrotreating integrated as claimed in claim 3 and steam pyrolysis method, wherein evaporate the liquid of described discharge
Divide and be blended with the pyrolysis fuel oil of recovery in step (g).
5. the hydrotreating integrated as claimed in claim 3 and steam pyrolysis method, wherein add the hydrogenation of described heating
It is to use to separate dress based on physics with the vapor-liquid of mechanical separation that the effluent of work is separated into vapor fraction with liquid distillate
Put.
6. the hydrotreating integrated as claimed in claim 5 and steam pyrolysis method, wherein said vapor-liquid separates dress
Put and include
Having the pre-rotation element of entering part and transition portion, described entering part has the hydrogenation for receiving described heating
The entrance of the effluent of processing and shaped form conduit,
Controlled eddy flow section, described eddy flow section has
The entrance to described pre-rotation element is adjoined by the meeting point of described shaped form conduit and described eddy flow section,
At the lifting pipeline section of the upper end of described eddy flow component, steam is by described lifting pipeline section；
And
Liquid header/settling section, liquid passes through described liquid header/settling section.
7. the hydrotreating integrated as claimed in claim 1 and steam pyrolysis method, wherein
Step (d) includes
The mix products stream of described thermal cracking is compressed with multiple compression stages；
The thermal cracking mix products making described compression flows through and is processed to produce hydrogen sulfide and the titanium dioxide with reduction by caustic alkali
The mix products stream of the thermal cracking of carbon content；
There is described in compression the mix products stream of the hydrogen sulfide of reduction and the thermal cracking of carbon dioxide content；
The mix products stream making the hydrogen sulfide with reduction of described compression and the thermal cracking of carbon dioxide content is dehydrated；
Flow back to receive from the mix products of the hydrogen sulfide with reduction of the compression of described dehydration and the thermal cracking of carbon dioxide content
Hydrogen；And
Surplus from the mix products stream of the hydrogen sulfide with reduction of the compression of described dehydration and the thermal cracking of carbon dioxide content
Remaining part is separately won such as the alkene in step (e) and aromatic compound and such as the pyrolysis fuel oil in step (f)；
And
Step (e) includes the hydrogen sulfide with reduction of the purification compression from described dehydration and the thermal cracking of carbon dioxide content
The hydrogen that mix products flows back to receive is for being recycled to described hydrogenation processing district.
8. the hydrotreating integrated as claimed in claim 7 and steam pyrolysis method, wherein from the compression of described dehydration
There is the mix products of the hydrogen sulfide of reduction and the thermal cracking of carbon dioxide content flow back to receive hydrogen and farther include to reclaim individually
Methane is for use as the burner in described cracking step and/or the fuel of heater.
Applications Claiming Priority (3)
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|---|---|---|---|
| US201261591816P | 2012-01-27 | 2012-01-27 | |
| US61/591,816 | 2012-01-27 | ||
| PCT/US2013/023337 WO2013112970A1 (en) | 2012-01-27 | 2013-01-27 | Integrated hydrotreating and steam pyrolysis process including residual bypass for direct processing of a crude oil |
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| CN104105783A CN104105783A (en) | 2014-10-15 |
| CN104105783B true CN104105783B (en) | 2016-11-23 |
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| US (1) | US20130197283A1 (en) |
| EP (1) | EP2807235B1 (en) |
| JP (2) | JP6151718B2 (en) |
| KR (1) | KR102061186B1 (en) |
| CN (1) | CN104105783B (en) |
| SG (1) | SG11201404387QA (en) |
| WO (1) | WO2013112970A1 (en) |
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| US9255230B2 (en) * | 2012-01-27 | 2016-02-09 | Saudi Arabian Oil Company | Integrated hydrotreating and steam pyrolysis process for direct processing of a crude oil |
| CN103699160B (en) * | 2013-12-24 | 2016-02-10 | 北京航天时代光电科技有限公司 | The quantitative level pressure feeding mechanism of a kind of high-precision gas |
| WO2015128042A1 (en) | 2014-02-25 | 2015-09-03 | Saudi Basic Industries Corporation | A method of controlling the supply and allocation of hydrogen gas in a hydrogen system of a refinery integrated with olefins and aromatics plants |
| WO2018142351A1 (en) | 2017-02-02 | 2018-08-09 | Sabic Global Technologies B.V. | A process for the preparation of a feedstock for a hydroprocessing unit and an integrated hydrotreating and steam pyrolysis process for the direct processing of a crude oil to produce olefinic and aromatic petrochemicals |
| US10689587B2 (en) * | 2017-04-26 | 2020-06-23 | Saudi Arabian Oil Company | Systems and processes for conversion of crude oil |
| WO2019036426A1 (en) * | 2017-08-15 | 2019-02-21 | Sabic Global Technologies, B.V. | Light olefin production via an integrated steam cracking and hydrocracking process |
| KR102732193B1 (en) | 2019-03-15 | 2024-11-19 | 루머스 테크놀로지 엘엘씨 | Method of mixing diluted steam with liquid hydrocarbon before steam cracking |
| CN113874475B (en) * | 2019-04-05 | 2023-10-27 | 鲁姆斯科技有限责任公司 | A method of converting crude oil and condensate into chemicals using a mixture of hydrogenation and decarbonization |
| US11279891B2 (en) * | 2020-03-05 | 2022-03-22 | Saudi Arabian Oil Company | Systems and processes for direct crude oil upgrading to hydrogen and chemicals |
| US20230151283A1 (en) * | 2020-04-20 | 2023-05-18 | Exxonmobil Chemical Patents Inc. | Hydrocarbon pyrolysis of feeds containing nitrogen |
| JP7089101B2 (en) * | 2021-09-27 | 2022-06-21 | 住友化学株式会社 | Hydrogen production method and production system |
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- 2013-01-27 KR KR1020147024066A patent/KR102061186B1/en active Active
- 2013-01-27 CN CN201380006610.6A patent/CN104105783B/en active Active
- 2013-01-27 JP JP2014554905A patent/JP6151718B2/en not_active Expired - Fee Related
- 2013-01-27 EP EP13710090.5A patent/EP2807235B1/en active Active
- 2013-01-28 US US13/751,395 patent/US20130197283A1/en not_active Abandoned
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| CN101292013A (en) * | 2005-10-20 | 2008-10-22 | 埃克森美孚化学专利公司 | Hydrocarbon resid processing and visbreaking steam cracker feed |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102061186B1 (en) | 2019-12-31 |
| JP2017197748A (en) | 2017-11-02 |
| JP6491260B2 (en) | 2019-03-27 |
| EP2807235A1 (en) | 2014-12-03 |
| KR20140138141A (en) | 2014-12-03 |
| JP6151718B2 (en) | 2017-06-21 |
| US20130197283A1 (en) | 2013-08-01 |
| SG11201404387QA (en) | 2014-10-30 |
| JP2015509128A (en) | 2015-03-26 |
| WO2013112970A1 (en) | 2013-08-01 |
| EP2807235B1 (en) | 2021-03-17 |
| CN104105783A (en) | 2014-10-15 |
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